JP3501883B2 - Vulcanized polyolefin plastelastomer composition and method for producing the same - Google Patents

Abstract

The invention provides plastoelastomer compositions obtained by dynamic vulcanization, in the presence of vulcanizing agents, of a polymeric mixture comprising: a) 15-70 wt% of polypropylene, b) 2-20 wt% of polyisobutene, c) 20-70 wt% of ethylene/propylene/diene elastomer terpolymer (EPDM), d) 0-35 wt% of ethylene/propylene elastomer copolymer (EPM), e) 3-30 wt% of polybutadiene.

Description

Detailed Description of the Invention

The present invention relates to dynamic vulcanization prepared plastoelastomer polymer compositions which provide an interesting combination of elasticity and thermoplasticity. The plastoelastomer mixture of the present invention comprises a plastomer thermoplastic matrix consisting essentially of polypropylene, and ethylene /
Propylene / diene (EPDM) terpolymer, polybutadiene, polyisobutene and optionally ethylene /
Obtained by dynamic vulcanization of an elastomeric matrix comprising a propylene (EPM) copolymer. The polymer composition of the present invention is a so-called thermoplastic elastomer (TP
E) and (TP) when the elastomer phase is vulcanized
V). However, recently, the name "dynamic vulcanization alloy" has been preferred. These compositions are generally such that the elastomeric portion crosslinks and is densely dispersed as a discontinuous phase in the continuous phase formed by the thermoplastic phase.
Obtained by mixing the vulcanized elastomer component with the thermoplastic component. DVA is prepared by vulcanizing the elastomeric component while mixing the elastomeric component with the plastomer component at a temperature at which the thermoplastic resin can achieve a plastic state.

Early work on the crosslinking of olefinic thermoplastic compositions was conducted by Gassler and Haslett in US-
A-3,037,954. This document introduces the concept of "dynamic cross-linking", whereby cross-linking into a non-cross-linked matrix of polymer resin is achieved by mixing the thermoplastic part with the elastomer part and simultaneously vulcanizing the elastomer phase. A final blend is obtained in which the elastomer is microgel dispersed and is referred to as a dynamically vulcanized alloy or DVA. US-A-3,03
7,954 describes a composition comprising polypropylene and rubber, such as butyl rubber, chlorinated butyl rubber, polybutadiene, polychloroprene or polyisobutene. These compositions are made from 50% polypropylene
It comprises 95% and 5% to 50% rubber. US-A
-3,758,643 and US-A-3,086,5
58 describes an olefinic thermoplastic elastomer comprising a thermoplastic polyolefin resin and a partially vulcanized olefin copolymer as the elastomer phase. Although these compositions are easy to process and have a good surface appearance, their use is limited because of their poor compression set values and unfavorable working temperatures. The limitation of these thermoplastics is directly due to the partial vulcanization of the elastomer phase. U by Coran et al.
S-A-4, 104, 210 and US-A-4, 13
No. 0,535 optimizes the DVA manufacturing process, and first complete vulcanization of the elastomer phase by dynamic vulcanization. This method overcomes limitations on physical and mechanical properties and achieves properties comparable to those of vulcanized rubber by conventional crosslinking methods.

By analyzing the properties of TPVs obtained using various types of thermoplastics and elastomers, the best combination of physico-mechanical properties of the materials in question is polypropylene and EP (D) M. It was found to be achieved by blending rubbers (AY Coran, thermoplastic elastomers, NRLegge, G. Holden and HE Sch.
roeder, publisher, New York 1987, p. 133).
In US-A-4,212,787 by Matsuda et al.
Partially dynamic vulcanization of a blend with a confirmed amount of an olefinic thermoplastic (polypropylene or polyethylene), an EPDM copolymer and a rubber that is not vulcanized with a peroxide, such as polyisobutene. A thermoplastic elastomer is manufactured by this,
The composition produced by mixing the three polyolefin polymers has a good surface appearance and at the same time provides sufficient heat resistance, tensile strength, flexibility and elastic recovery. US-A-4,202,801 by Petersen
Olefinic thermoplastic resin, EPM copolymer or EP
Dynamic partial vulcanization of a mixture of a DM terpolymer and an unsaturated olefin rubber, ie a polymer obtained by polymerizing or copolymerizing monomers having conjugated double bonds (eg polyisoprene, polybutadiene or polychloroprene). Discloses a blend obtained by This thermoplastic has good compression set and high tensile strength at elevated temperatures. US-A-4,616,052 by Habibullah is a polymer blend of polypropylene and dynamically vulcanized EPDM terpolymer (65% -90%) as the main component, a butyl rubber group rubber (5% as the second main component). % To 20%) and 1 to 20% by weight of polyisobutene as a plasticizer. Although this composition has a high resistance to creep at high temperatures, it has the disadvantage that its production requires one more step than other plastomeric compositions.

Here, according to the present invention, all the above-mentioned desirable properties (good surface appearance, satisfactory surface appearance) can be produced in a single operation step and without defects resulting from only partial vulcanization of the crosslinkable elastomer phase. An olefinic thermoplastic elastomer composition has been developed in which the elastomeric portion is virtually completely (dynamically) vulcanized, having excellent compression set, high heat resistance, and excellent tear strength. In particular, it has an elastic recovery rate that is far superior to that found in prior art plastoelastomer compositions, while at the same time providing the typical properties of classical dynamically vulcanized thermoplastic polymer elastomer alloys. A composition was found that retained all. A dynamically vulcanized plastoelastomer composition according to the invention comprising: a) a degree of vulcanization and / or grafting of from 5 to 50.
%, Preferably 10-40% polypropylene,
Or 15-70% by weight, preferably 20-60% by weight, of copolymers of propylene and other alpha-olefins with a maximum amount of alpha-olefins of 15%, preferably 10%, b) virtually vulcanized Polyisobutene 2
-20% by weight, preferably 4-15% by weight, c) ethylene / propylene / diene elastomer terpolymer (EPDM) 20-70% by weight, preferably 30.
~ 60 wt%, d) ethylene / propylene / elastomer copolymer (E
PM) 0-35% by weight, preferably 3-30% by weight, and e) polybutadiene 3-30% by weight, preferably 5-2.
0% by weight, the sum of components c), d) and e) being vulcanized to an average of more than 92%, preferably more than 95%, and optionally an extender oil in the composition, A composition is provided which is added in an amount of 5 to 60% by weight, preferably 10 to 55% by weight, relative to the composition.

The degree of vulcanization (this term also includes all grafting) is determined by xylene extraction as described in US-A-4,963,612. When vulcanizing a certain percentage, eg 15%, of a polymeric material, it means that 15% of this material is insoluble in xylene at 135 ° C. The term "practically unvulcanized"
Means that the degree of vulcanization and / or grafting is 5% or less. As is well known, the performance level of vulcanized thermoplastic elastomers is, as already mentioned, closely related to the structure of the DVA and the type of vulcanization of the dispersed elastomer layer. Here, polypropylene, polyisobutene, polybutadiene, E having suitable characteristics
By using the PDM terpolymer and optionally the EPM in the correct proportions, the dispersity of the elastomer phase in the plastomer phase and the crosslinking of the elastomer phase are best matched. As a result, the mechanical properties and elasticity of the thermoplastic elastomer are optimized. The above composition optionally of non-polymeric inorganic and / or organic substances, for example _{ZnO, SiO 2, TiO 2,} CaCO 3, BaS
O ₄ , kaolin, carbon black, stabilizers, antiaging agents, catalysts, and vulcanization aids and accelerators may also be included. As with other plast elastomer compositions, the compositions of the present invention also consist essentially of an elastomer phase dispersed in a plastic phase that functions as a continuous phase,
The elastomeric phase consists of particles less than 10 μm in size, with at least 50% of the particles having a size less than 5 μm.

In addition to the usual properties of known plastoelastomer compositions, the compositions of the present invention have a fast recovery rate of applied deformation (as can be seen from the examples). This allows the composition of the present invention to be used more effectively than prior art DVA in the following applications: -Motion transmission belt. Less energy dissipation due to internal friction, i.e. the compositions of the invention have a longer life and shelf life-synthetic flooring. Elastic recovery is faster-sole. Reduce energy dissipation-Shock absorbers for ships. Impact absorption of collisions-Other uses that require rapid absorption of dynamic stress without significant deformation Regarding the polymers included in the composition of the present invention, the polypropylene used may be a homopolymer or up to 15%.
Up to, preferably up to 10% other alpha-
It may be a copolymer containing an olefin. Polyisobutene preferably has a high fluidity (viscosity 2.
6-3.8 dl / g). EPDM terpolymer is 20-6
0% by weight, preferably 25-45% by weight of polypropylene, 40-75% by weight of ethylene, and 2-11% by weight of dienes such as 1,3-butadiene, 1,4-hexadiene, norbornadiene, ethylidene-norbornene. , Or dicyclopentadiene. The EPM copolymer may contain 20 to 60% by weight, preferably 20 to 45% by weight of propylene, and usually has a weight average molecular weight of more than 2 × 10 ⁵ , and Mw / Mm <
2.7 and r1 × r2 ≦ 0.8.

EPM copolymers and EPDM terpolymers are preferably prepared by polymerization using a Ziegler-Natta catalyst, although related processes are known in the art. Examples of Ziegler-Natta catalysts include compounds of metals belonging to Group IVa, Va, VIa, or VIIa of the periodic table of elements, such as Ti, V, Zr, or Cr, and I, II of the periodic table of elements. , A metal belonging to the group IIIA or IIIB,
A catalyst prepared by contacting or pre-contacting with an organometallic compound containing at least one metal-carbon bond, such as an aluminum alkyl or a partially halogenated or oxygenated aluminum alkyl. Compounds of elements of group IVa, Va, VIa or VIIa are unsupported or supported on known inert or active substrates, halides, alcoholates,
It may be an allene derivative or another organometallic derivative. The polybutadiene used is preferably of high structural purity, ie having a cis content of> 95%, preferably> 98%. Polybutadiene with a high cis content is preferably produced using a Ziegler-Natta catalyst. The extender oil may be aromatic, naphthenic or paraffinic, but is preferably paraffinic.

The plastoelastomer composition of the present invention comprises
By mastication or other similar operation in which energy is applied by shear in the presence of a vulcanizing system (peroxide and desired auxiliaries): a) 15-70% by weight polypropylene, preferably 20
-60% by weight, b) 2-20% by weight of polyisobutene, preferably 4-1
5% by weight, c) 20 to 70% by weight of ethylene / propylene / diene elastomer terpolymer (EPDM), preferably 30
~ 60% by weight, d) ethylene / propylene elastomer copolymer (EP
M) 0-35% by weight, preferably 3-30% by weight, and e) polybutadiene 3-30% by weight, preferably 5-2.
Made from a polymer mixture comprising 0% by weight and having a total percentage of components a) to e) of 100. Extender oil is preferably added to the composition in an amount of 5 to 60% by weight, preferably 10 to 55% by weight, based on the total of polymers a) to e). The properties of the polymers a) to e) are as described above.

Three typical vulcanizing compositions (A),
(B) and (C) are shown below. Composition (A):-Polypropylene: 25% by weight-Polyisobutene: 6% by weight-Ethylene / propylene / ethylidene-norbornene elastomer terpolymer (EPDM): 50% by weight-Ethylene / propylene elastomer terpolymer (E)
PM): 13% by weight, -Polybutadiene: 6% by weight, -Extender oil: 42 with respect to the total polymer components
weight%. Composition (B):-Polypropylene: 25% by weight-Polyisobutene: 13% by weight-Ethylene / propylene / ethylidene-norbornene elastomer terpolymer (EPDM): 37% by weight-Ethylene / propylene elastomer terpolymer (E
PM): 12% by weight, -Polybutadiene: 13% by weight, -Extender oil: 42 with respect to the total of the polymer components
weight%. Composition (C):-Polypropylene: 35% by weight-Polyisobutene: 6% by weight-Ethylene / propylene / ethylidene-norbornene elastomer terpolymer (EPDM): 47% by weight-Polybutadiene: 12% by weight-Extender oil: 30 based on total polymer components
weight%.

The above composition is dynamically vulcanized at a temperature at which polypropylene is melted and at least 92%, preferably at least 95% vulcanization of the initial EPR rubber and polybutadiene occurs. The extender oil can be added to the above components during mixing, with and / or separately from any of the components that are oil extended. The composition may contain up to 4% by weight of polyethylene.
The vulcanizing agent used is a peroxide, preferably within the vulcanizing temperature range, ie 100-240 ° C., with a half-life of 10-20.
It is a peroxide that is 0 seconds. Examples of peroxides that can be used in the vulcanization process are dicumyl peroxide, α, α′-bis (t
-Butylperoxy) -m- and / or -p-diisopropylbenzene, and 1,1-di-t-butylperoxide-3,5,5-trimethylcyclohexane, but other organic peroxides having the above decomposition rates. Oxides can also be used. The amount of peroxide used for vulcanization is generally 0.1 to 10% by weight, preferably 0.2 to 5% by weight, based on the polymer composition. In addition to vulcanizing agents, all known auxiliaries that can perform the desired function, such as furan derivatives, 1,5-difurfuryl-1,4-pentadiene-3.
-One and difurfuraldiazine can be used. These auxiliaries are 5% based on the peroxide used.
It is used in an amount of -60% by weight, preferably 10-30% by weight.

Another aspect of the present invention is a method for producing the vulcanized polyolefin-based plast elastomer composition of the present invention, which comprises: 1) a) polypropylene 15 to 70% by weight, preferably 20 to 60% by weight, b ) 2 to 20% by weight of polyisobutene, preferably 4 to 1
5% by weight, c) 20 to 70% by weight of ethylene / propylene / diene elastomer terpolymer (EPDM), preferably 30
~ 60% by weight, d) ethylene / propylene elastomer copolymer (EP
M) 0-35% by weight, preferably 3-30% by weight, and e) polybutadiene 3-30% by weight, preferably 5-2.
A homogeneous polymer mixture comprising 0% by weight and having a total percentage of components a) to e) of 100, said polymer mixture being f) 5 to 60% by weight, based on the polymer composition, Extender oil, preferably in an amount of 10 to 55% by weight, g) as a vulcanizing agent, 0.1 to 10% by weight, based on the sum of the copolymer (EPM), terpolymer (EPDM) and polybutadiene (c + d + e). Amount of organic peroxide, and h) adding vulcanization aid in an amount of 10 to 60% by weight with respect to peroxide (g), and 2) when mixing or masticating or applying other shearing force. In addition, the mixture has a degree of crosslinking (c + d + e) of vulcanizable elastomers present of more than 92%, preferably more than 95% and a degree of crosslinking of polypropylene of 5-5.
Up to 0%, preferably 10-40%, 160-2
A method comprising the step of heating to a temperature of 40 ° C.

The temperature of 160-240 ° C. in step 2) is necessary to completely melt the polypropylene. Oil extended EPR terpolymers and / or copolymers can also be used, in which case the oil in section f) can be reduced or eliminated. By changing the vulcanization conditions within the range of the above production method, it is possible to obtain products in which the ratio of the vulcanized portion after crosslinking to the non-vulcanized portion is different. In particular, for example, the percentage of crosslinked or grafted polypropylene can be adjusted by varying the concentrations of peroxide and crosslinking coagent. The vulcanized fraction is a graft of the elastomeric components c), d), substances derived from the vulcanization of e) and part of the polypropylene, and optionally also of the same component, vulcanized or not. Comprising a substance derived from. To modify the product hardness, various amounts of polypropylene and / or further extender oil can be added after the dynamic vulcanization step 2).

The following examples illustrate the invention in more detail, but do not limit it. Examples In the examples below, the elastomer, plastomer, vulcanizing components, processing aids and desired fillers are placed in a suitable mixer in the required ratios. The mixer may be, for example, a Banbury internal mixer or other device capable of achieving sufficient mastication at the required temperature. The device may be preheated to reduce the time required to obtain the desired temperature range. The preheating temperature must be lower than the decomposition temperature of the vulcanizing agent used. During mixing, the temperature is raised above the decomposition temperature of the vulcanizing agent. Mixing typically continues for a long enough time to ensure that at least 95% of the vulcanization system has decomposed and the mixture is thoroughly mixed. After the mixture has been processed to the desired degree, it is possible to add any components that have not yet been added. In this case, the mixing is continued until the components are completely mixed. The mixture is then removed from the mixer and, if desired, transferred to an open mixer to form a sheet for granulation if desired. These materials can be used to form articles of suitable shape by extrusion, injection molding or other suitable manufacturing method.

The vulcanized polyolefin thermoplastic elastomer composition was evaluated using test pieces produced by injection molding to obtain typical chemical and physical properties of products of this type. To evaluate the elastic recovery of the synthesized thermoplastics, a hysteresis cycle was performed to determine the energy dissipated and stored energy by the material during the load-relaxation cycle by the Rubber Chem. Techn.
ol., 21, 281 (1948). The ratio of the energy used to stretch the specimen to a predetermined length (100%) and the energy associated with the elastic recovery stage is closely related to the elastic quality of the material. The vulcanization percentage of the crosslinkable elastomer component is U
It was evaluated by measuring the insoluble residue after extraction for 5 hours in boiling xylene (135 ° C.) as described in SA-4,963,612. The non-crosslinked fraction was calculated taking into account the amount of inert filler introduced and the polymeric material soluble in boiling xylene. All tests were performed using the general procedure described above. The EPDM terpolymer used had a propylene content of 28% by weight and an ethylene content of 68.
% And ethylidene-norbornene content 4%, Mooney viscosity ML (1 + 4) 125 43, paraffin oil content 40%. The EPM copolymer has a propylene content of 26%, r1xr2 = 0.8, and a Mooney viscosity (1
+4) 125 is 72, Mw / Mn = 2.6 and Mw =
It is 2x10 ⁵ . Polypropylene contains about 4% ethylene and about 6% benzene distributed in an irregular order in the polymer chain and has a fluidity (230 ° C. and 2160 grams,
ASTM D 1238. L) 6 dg / min, density 0.9 g / cm
³ and melting point 135 ° C. The polyisobutene used had an intrinsic viscosity in diisobutylene of 3.7 dl / g,
The density is 0.92 g / cm ³ . The butadiene rubber used has a Mooney viscosity (1 + 4) 100 of 43 and a cis-microstructure content of> 98%. The vulcanization system used is
It was Peroximon F40 in combination with 1,5-difurfuryl-1,4-pentadien-3-one.

To carry out the tests shown in Table 1, 1
The mixture was placed in a Banbury internal mixer preheated to 10 to 120 ° C. Usually, after 3-4 minutes, the energy peak associated with the change in viscosity of the mixture following vulcanization of the elastomer phase is recorded. Mixing continues for a further 3-4 minutes. The temperature change recorded during the test, measured by a thermocouple placed on the wall of the mixing chamber, is usually 90 ° C. In addition to the polymer components and vulcanization system expressed in parts by volume, all compositions related to the examples described contain a total of 60 mineral fillers, anti-aging agents and other process and product additives. Includes phr (part / rubber 100 parts). In order to make the data relating to stored energy more comparable, all plastoelastomer compositions of the described examples contain the same percentage of extender oil. That is, fluctuations caused by different amounts of oil-extended EPDM terpolymer were corrected by adding a calculated amount of pure oil. Examples 5 and 6 form part of the invention, while all other examples with the letter C are included for comparison purposes. The compositions related to the described examples are all above 95% of the crosslinkable elastomeric fraction, with the exception of composition C8, whose properties had to be measured on a thermoplastic mixture which was not completely vulcanized. It showed vulcanization. The data are shown in Tables 1 and 2. In Table 1, EPDM indicates the amount of pure terpolymer (ie, ignoring the amount of oil normally diluted), PP
Represents polypropylene, BR represents polybutadiene, PIB represents polyisobutene, paraffin oil represents (pure paraffin oil + oil forming an EPDM solution in oil),% pl / el is the plastomer composition relative to the elastomer composition. The product is expressed in% by weight. In Table 2,
Permanent elongation represents% permanent elongation at 75 and compression set represents% compression set after 22 hours at 100.degree.

Examples 1C and 2C In Examples 1C and 2C, (EP
Two thermoplastic elastomer compositions were prepared by adding 10 and 20 phr of cis-polybutadiene to M + EPDM + PP, respectively (see Table 1). With respect to the composition of the product after vulcanization, the composition of Example 1C (percentages are based on the total polymer composition, thus 100% means the total polymer soluble and insoluble in xylene) is as follows: On the street. a) Residue insoluble in xylene at 135 ° C. was vulcanized (EPM + EPDM + polybutadiene (PB)) = 72
%, Polypropylene (PP) = 4%, b) The part soluble in xylene at 135 ° C. is polypropylene = 21%, unvulcanized (EPM + EPDM + PB) = 3%.
Consists of. The vulcanizable elastomer (EPM + EPDM + PB) has a% vulcanization of 96% and the final product contains 42% (based on 100% total polymer) of extender oil. For the composition of Example 2C: a) the residue insoluble in xylene at 135 ° C. consists of vulcanized (EPM + EPDM + PB) = 74%, polypropylene = 6%, b) the soluble part is PP = 18%, Unvulcanized (EPM + EP
DM + PB) = 4%. The vulcanizable elastomer (EPM + EPDM + PB) has a% vulcanization of 98% and the final product contains 41% extender oil. The stored energy values (see Table 2) for Examples 1C and 2C were calculated using the rubber EPM as elastomer.
The effect of polybutadiene on the improvement of elastic recovery is clear when compared with the values of composition C7 prepared using only and EPDM. In this regard, storage energy has increased from 30.8 to 32.8, to 34.7%.

Examples 3C and 4C Examples 3C and 4C repeat the composition of Examples 1 and 2, but with polybutadiene in the form of polyisobutene (PIB).
Is replaced by. For the composition of Example 3C: a) the residue insoluble in xylene at 135 ° C. consists of vulcanized (EPM + EPDM + PB) = 65%, polypropylene = 5%, b) the soluble part is PP = 20%, Unvulcanized (EPM + EP
DM + PB) = 4%, polyisobutene = 7%. The vulcanizable elastomer (EPM + EPDM + PB) has a% vulcanization of 95% and the final product contains 42% extender oil. For the composition of Example 4C: a) The residue insoluble in xylene at 135 ° C. consists of vulcanized (EPM + EPDM + PB) = 59%, polypropylene = 4%, b) the soluble part is PP = 21%, Unvulcanized (EPM + EP
DM + PB) = 3%, polyisobutene = 13%. The vulcanizable elastomer (EPM + EPDM + PB) has a% vulcanization of 95% and the final product contains 42% extender oil. Comparing the storage energy values for these examples (see Table 2) with the values of composition C7 prepared using only rubber EPM and EPDM as elastomers, limiting the amount of polyisobutene to 10 phr It can be seen that the value increases, but when it reaches 20 phr, this value decreases. This change is probably due to the fact that above 10 phr polyisobutene, the positive effect of this component is negatively affected by the reduced amount of vulcanized rubber.

Examples 5 and 6 In Examples 5 and 6, polybutadiene and polyisobutene are used simultaneously to produce a vulcanized thermoplastic mixture. Particularly, in Example 5, each component was 1
0 phr was used, whereas in Example 6 this amount was 20 p
It was hr. Regarding the composition of Example 5, a) the residue insoluble in xylene at 135 ° C. consists of vulcanized (EPM + EPDM + PB) = 66%, polypropylene = 5%, b) the soluble part is PP = 21%, Unvulcanized (EPM + EP
DM + PB) = 3%, polyisobutene = 6%. The vulcanizable elastomer (EPM + EPDM + PB) has a% vulcanization of 96% and the final product contains 41% extender oil. With respect to the composition of Example 6, a) the residue insoluble in xylene at 135 ° C. consists of vulcanized (EPM + EPDM + PB) = 61%, polypropylene = 6%, b) the soluble part is PP = 19%, Unvulcanized (EPM + EP
DM + PB) = 2%, polyisobutene = 12%. The vulcanizable elastomer (EPM + EPDM + PB) has a% vulcanization of 96% and the final product contains 41% extender oil. Analysis of the storage energies of these compositions shows that Example 5 is a further improvement over the preceding examples. In particular, by comparing Production C7, which does not contain both polybutadiene and polyisobutene, with Example 5, the storage energy is 36.3% against a base value of 30.8%. Compared to Example 5, the composition of Example 6 has a significantly lower storage energy value and the amount of EPM and EPDM rubber is clearly lower compared to the total elastomer fraction.

Comparative Examples C7 and C8 In Composition C7, the elastomer components were EPM and EP.
Only DM rubber. Composition C8 was prepared to confirm the effect of the degree of crosslinking of the vulcanizable rubber. In particular, using the manufacturing method already described, composition C8 was manufactured in the same manner as composition 5 except for the concentration of the vulcanization system.
With respect to the composition of Example 7C, a) the residue insoluble in xylene at 135 ° C. consists of vulcanized (EPM + EPDM + PB) = 73%, polypropylene = 5%, b) the soluble part is PP = 20%, Unvulcanized (EPM + EP
DM + PB) = 3%, polyisobutene = 3%. The vulcanizable elastomer (EPM + EPDM + PB) has a% vulcanization of 96% and the final product contains 42% extender oil. For the composition of Example 8C: a) the residue insoluble in xylene at 135 ° C. consists of vulcanized (EPM + EPDM + PB) = 61%, polypropylene = 3%, b) the soluble part is PP = 22%, Unvulcanized (EPM + EP
DM + PB) = 9%, PIB = 6%. The vulcanizable elastomer (EPM + EPDM + PB) has a% vulcanization of 89% and the final product contains 41% extender oil. By comparing the storage energy of composition C8, ie 26.7%, with the storage energy of fully vulcanized composition 5, ie 36.3%, the material of this parameter (ie degree of vulcanization) The fundamental effect of the on the elastomeric properties is clear.

[0020]

In order to demonstrate the heat resistance of the compositions of the present invention, the products of Examples 5 and 6 were subjected to 5 treatment cycles, namely product manufacture and subsequent retreatment above their melting point. Example 5: Shore A 64-66, tensile strength 4.6-
4.4, ultimate elongation 212-205, tear strength 24-2
6, permanent elongation 8-10, compression set 39-41. Example 6: Shore A 64-65, tensile strength 3.9-
3.8, ultimate elongation 225-219, tear strength 20.1
-21.2, permanent elongation 8-9.5, compression set 45
-46. The above property changes are of limited importance and are therefore comparable to the values found in similar products of the prior art.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventors Patrizia, Piancastelluri Bologna, Biale, Oriani, Italy, 40/2 (72) Inventors Giann, Antonio, Suggesté Ferrara, Via, Pomposa, 33 (72) 72) Inventor Roger, Lionette Brussels, Ryu, Van, Elmont, Belgium 11 (56) References JP-A-53-47446 (JP, A) JP-A-54-100443 (JP, A) JP-A-63 −33451 (JP, A) (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08L 1/00-101/16 C08K 3/00-13/08 C08J 3/24

Claims (16)

(57) [Claims] 1. A dynamically vulcanized plastoelastomer composition comprising: a) a degree of vulcanization and / or grafting of 5 to 50%.
15 to 70% by weight of polypropylene, or a copolymer of propylene and other alpha olefins with a maximum amount of 15% of alpha olefins, b) virtually no vulcanized polyisobutene 2
20 to 70% by weight, c) 20 to 70% by weight of ethylene / propylene / diene elastomer terpolymer (EPDM), d) ethylene / propylene / elastomer copolymer (E)
PM) 0 to 35% by weight and e) polybutadiene 3 to 30% by weight, wherein the sum of components c), d) and e) has been vulcanized to an average of more than 92% and component a ) -E) the sum of the percentages is 100, optionally with an extender oil in the composition of 5 to 60% by weight, based on the composition.
The composition is added in an amount of. 2. A) Polypropylene having a degree of vulcanization and / or grafting of 10 to 40%, or a copolymer of propylene and another alpha olefin having a maximum amount of 10% of an alpha-olefin of 20 to 20%. 60% by weight, b) virtually no vulcanized polyisobutene 4
~ 15 wt%, c) 30-60 wt% ethylene / propylene / diene elastomer terpolymer (EPDM), d) ethylene / propylene / elastomer copolymer (E
PM) 3 to 30% by weight, and e) polybutadiene 5 to 20% by weight, and the total of components c), d) and e) is vulcanized to an average of more than 95% and component a The composition according to claim 1, wherein the total percentage of) -e) is 100 and optionally extender oil is added to the composition in an amount of 10-55% by weight relative to the composition. 3. A composition according to claim 2, wherein the polypropylene comprises 4% ethylene and 6% butene. 4. A composition according to claim 1, wherein the polybutadiene has a cis content of more than 95%. 5. The composition of claim 4, wherein the polybutadiene has a cis content of greater than 98%. 6. The EPDM terpolymer is propylene 20.
The composition of claim 1 comprising .about.60% by weight, 40 to 75% by weight ethylene, and 2 to 11% by weight diene. 7. The EPDM terpolymer is propylene 25.
7. The composition of claim 6, comprising .about.45% by weight. 8. The EPM copolymer is propylene 20-60.
The composition of claim 1, wherein the composition comprises wt%. 9. The EPM copolymer is propylene 20-45.
9. The composition according to claim 8, wherein the composition comprises wt%. 10. In addition to fillers, extender oils, vulcanizing agents and vulcanization aids, a) polypropylene 15-70% by weight, b) polyisobutene 2-20% by weight, c) ethylene / propylene / diene elastomer tar. Polymer (EPDM) 20 to 70% by weight, d) Ethylene / propylene elastomer copolymer (EP
M) 0 to 35% by weight and e) 3 to 30% by weight of polybutadiene, the total percentage of components a) to e) being 100, a polymer mixture to be vulcanized. 11. A) 20 to 60% by weight of polypropylene, b) 4 to 15% by weight of polyisobutene, c) 30 to 60% by weight of ethylene / propylene / diene elastomer terpolymer (EPDM), and d) ethylene / propylene elastomer co-weight. Combined (EP
The polymer mixture according to claim 10, comprising M) 3 to 30% by weight and e) 5 to 20% by weight of polybutadiene, and the total percentage of components a) to e) is 100. 12. A) 25% by weight of polypropylene, b) 6% by weight of polyisobutene, c) 50% by weight of ethylene / propylene / ethylidene-norbornene elastomer terpolymer (EPDM), d) an ethylene / propylene elastomer copolymer (EP).
Polymer mixture according to claim 11, comprising M) 13% by weight and e) 6% by weight of polybutadiene. 13. A) 25% by weight polypropylene, b) 13% by weight polyisobutene, c) 37% by weight ethylene / propylene / ethylidene-norbornene elastomer terpolymer (EPDM), d) an ethylene / propylene elastomer copolymer (EP).
Polymer mixture according to claim 11, comprising M) 12% by weight and e) 13% by weight of polybutadiene. 14. A composition comprising a) 35% by weight polypropylene, b) 6% by weight polyisobutene, c) 47% by weight ethylene / propylene / ethylidene-norbornene elastomer terpolymer (EPDM), and d) 12% by weight polybutadiene. The polymer mixture according to claim 11. 15. A) a) polypropylene 15-70% by weight, b) polyisobutene 2-20% by weight, c) ethylene / propylene / diene elastomer terpolymer (EPDM) 20-70% by weight, d) ethylene / propylene elastomer. Copolymer (EP
M) 0 to 35% by weight and e) 3 to 30% by weight of polybutadiene, a homogeneous polymer mixture having a total percentage of components a) to e) of 100 is prepared. f) extender oil in an amount of 5 to 60% by weight, based on the polymer composition, g) as a vulcanizing agent, 0 relative to the sum of copolymer (EPM), terpolymer (EPDM) and polybutadiene (c + d + e). 1) an organic peroxide in an amount of 1 to 10% by weight, and h) adding a vulcanization aid in an amount of 10 to 60% by weight with respect to the peroxide (g), and B) mixing or masticating or Upon application of another shearing force, the mixture obtained in step A) has a degree of crosslinking of 92% of the total (c + d + e) of vulcanizable elastomeric components present.
And a step of heating to a temperature of 160 to 240 ° C. until the degree of crosslinking of polypropylene becomes 5 to 50%. 16. A) a) 20 to 60 wt% polypropylene, b) 4 to 15 wt% polyisobutene, c) 30 to 60 wt% ethylene / propylene / diene elastomer terpolymer (EPDM), and d) ethylene / propylene elastomer. Copolymer (EP
M) 3 to 30% by weight and e) 5 to 20% by weight of polybutadiene, a homogeneous polymer mixture having a total percentage of components a) to e) of 100 is prepared. f) extender oil in an amount of 10 to 55% by weight with respect to the polymer composition, g) as a vulcanizing agent, based on the total of copolymer (EPM), terpolymer (EPDM) and polybutadiene (c + d + e). 1) an organic peroxide in an amount of 1 to 10% by weight, and h) adding a vulcanization aid in an amount of 10 to 60% by weight with respect to the peroxide (g), and B) mixing or masticating or Upon application of another shearing force, the mixture obtained in step A) has a degree of crosslinking of 95% of the total (c + d + e) of vulcanizable elastomeric components present.
16. The method according to claim 15, comprising the step of heating to a temperature of 160 to 240 ° C. until the polypropylene has a degree of crosslinking of 10 to 40%.